Studies on the Glycosylation of N-Acetylneuraminic Acid

Abstract

Glycal derivatives of N-acetylneuraminic acid were prepared and their N-iodosuccinimide-mediated glycosylation shown to proceed only with most reactive alcohols, Their reduced enol ether reactivity is attributed to the α unsaturated ester reature. Thus several reduced glycal derivatives were synthesized. These couid be glycosyiatec with simple alcohols as well as otner saccnarides as aglycones in averaae to modest yields with the trans-diaxiai additions compounas prevailing. A number or selective and specific prepparation led to both the anomeric phenylthioglycosides or N dcety Ineuraminic acid. These could be used in phenylmercurl triflate-promoted glycosylations to afford several derivatives.     

Modified Borohydride Agents1a-d Methyltriphenylphosphonium Tetrahydroborate; MePh3P+BH4 − as a Selective and An Efficient Reducing Agent

Abstract

MePh₃P⁺BH₄ ^? is able to reduce aldehydes and ketones to their corresponding alcohols in CH₂Cl₂. Aldehydes are reduced with high selectivity in the presence of ketones. α,β-Unsaturated carbonyl compounds undergo 1,2-reduction and produce their corresponding allylic alcohols in high yields. Carboxylic acid chlorides are also converted to their alcohols with high yields.     

Facile and Efficient Method for the Prins Reactions of Styrenes and Homoallyl Alcohols to 1,3‐Dioxanes and 4‐Tetrahydropyranols Using Bismuth(III) Triflate

Abstract

Bismuth(III) triflate has been found to be an efficient catalyst for the Prins reactions of styrenes and homoallyl alcohols, the reaction proceeds rapidly and affords the corresponding 1,3‐dioxanes and tetrahydropyran‐4‐ol in good yields. Scope and limitations of the styrenes and homoallyl alcohols are reported.     

Detailed studies on the reduction of aliphatic 3-, 4-, 6-, and 13-oximino esters: Synthesis of novel isomeric amino esters,oximino alcohols,and amino alcohols

The preparation of novel 3-, 4-, 6-, and 13-amino-tetradecanoic acid methyl esters (2a–d) obtained by the reduction of 3-, 4-, 6-, and 13-oximino-tetradecanoic acid methyl esters (1a–d), was investigated. Oximino esters were reduced to afford the corresponding amino esters using NaBH₄–ZrCl₄ reducing system with good yields (58–82%). However, the reduction of oximino esters with LiAlH₄ and BH₃. Tetrahydrofuran gave the corresponding novel 3-, 4-, 6-, and 13-oximino alcohols (3a–d), and 3-, 4-, 6-, and 13-amino alcohols (4a–d) respectively with good chemical yields.     

Lacunary Derivative [HPW9O34]8− as Reusable and Active Catalyst for Alcohol Oxidation in Water

Abstract

An effective and reusable catalytic system for the oxidation of alcohols was developed based on ?-Na₈HPW₉O₃₄. The oxidation was conducted in water using hydrogen peroxide as oxidant. Good yields of ketones were obtained in oxidation of secondary alcohols, and the catalyst was recycled 10 times without obvious loss in activity.     

Efficient and mild swern oxidation using a new sulfoxide and bis(trichloromethyl)carbonate

A new type of sulfoxide, 4-(2-(2-(methylsulfinyl) ethyl)-4-nitrophenyl)- morpholine (I), was designed and prepared in good yield. Upon the combination of I and bis(trichloromethyl)carbonate, the Swern oxidation of primary and secondary alcohols was significantly promoted under mild conditions, which afforded the corresponding aldehydes or ketones in good yields. It is noteworthy that the reoxidation of the isolated by-product sulfide V could be further recycled in Swern oxidation.     

New Application of N-Halosuccinimide/PPh3 for the Halogenation of Propargyl Alcohols to Haloallenes

An efficient and convenient new method has been developed for the preparation of haloallenes from propargyl alcohols by a reagent combination of N-halosuccinimide and triphenylphosphine. Chloroallenes 2 and bromoallenes 3 were obtained exclusively in moderate to good yields with regioselectivity.     

A Rapid and Convenient Synthesis of Homoallylic Alcohols by the Barbier‐Grignard Reaction

Abstract

The use of the Barbier‐Grignard reaction, where premixed allyl bromide and the carbonyl compound are added to magnesium in ether, is reported for the synthesis of homoallylic alcohols. This reaction provides good to excellent yields of most homoallylic alcohols with minimal formation of Wurtz coupling products.     

Synthesis of Chiral Sulfamide–Amine Alcohol Ligands for Enantioselective Alkylation of Aldehydes

A series of chiral sulfamide–amine alcohols (SAA) (1–6) has been easily synthesized from commercially available chiral amino alcohols. In the absence of Ti(O ⁱ Pr)₄, ligand 4 catalyzed the asymmetric addition of diethylzinc to aromatic aldehydes with moderate to good yields and enantioselectivities.     

Silica Chloride (SiO2-Cl), a New Heterogeneous Reagent,for the Selective and Efficient Conversion of Benzylic Alcohols to Their Corresponding Chlorides and Iodides

Abstract

Structurally different benzylic alcohols were efficiently converted to their corresponding chlorides by silica chloride (SiO₂-Cl) in CHCl₃ at room temperature. Silica chloride is also able to convert benzylic alcohols to their iodides in the presence of NaI in a mixture of CH₃CN/CHCl₃ in excellent yields.     

Enantioselective Catalytic Borane Reductions of Achiral Ketones: Synthesis and Application of New Rigid Catalysts Prepared from (R)-Phenylglycine and (S)-Phenylalanine

Exnantiocontrolled reduction of prochiral ketones with borane in the presence of homochiral amino alcohols 1 - 4 as enantioselective catalysts afforded the chiral corresponding secondary alcohols in moderate to high (55 to 88 %) optical yields.     

Nucleophilic Addition of Ytterbium Metal Umpoled Diaryl Ketones to Imines

Abstract

Cross-coupling reactions of diaryl ketones with imines promoted by ytterbium metal were described. β-Amino alcohols were prepared in good yields under mild and neutral conditions.     

PREPARATION OF FORMIC ACID ESTERS WITH A PHOSPHONIUM SALT AND ZINC BROMIDE IN N,N-DIMETHYLFORMAMIDE

ABSTRACT

When primary and secondary alcohols were treated with the phosphonium salt 1 and ZnBr₂ in N,N-dimethylformamide, the corresponding formic acid esters were obtained in good yields.     

Enantioselective Catalytic Borane Reductions of Achiral Ketones: Synthesis and Application Of New Catalysts Prepared from (S)-Tert-Leucine and (S)-Azetidinecarboxylic Acid

Enantiocontrolled reduction of prochiral ketones with borane in the presence of homochiral amino alcohols 1—3 as enantioselective catalysts afforded the corresponding secondary alcohols in moderate to high (69 to >99 %) optical yields.     

HIGHLY REGIOSELECTIVE AND STEREOSELECTIVE RADICAL ADDITION OF p-TsBr TO α-ALLENIC ALCOHOLS AND THEIR ELIMINATION REACTION: SYNTHESIS OF β-p-TOSYL-SUBSTITUTED α,β-UNSATURATED KETONES

ABSTRACT

Regio- and stereoselective radical addition of α-allenic alcohols with p-TsBr in the presence of a catalytic amount of AIBN afforded (E)-γ-bromo-β-sulfonyl allylic alcohols in moderate yields. The base-promoted 1,4-elimination followed by isomerization to give β-sulfonyl-α,β-unsaturated ketones is described.     

Enantioselective Catalytic Borane Reduction of Prochiral Ketones: Synthesis and Application of New Rigid β-Amino Alcohols with a Cycloalkanol Subunit

Enantiocontrolled reduction of prochiral ketones with borane in the presence of new enantiomerically pure bi-and tricyclic β-sec-amino alcohols 2–5 as stereodifferentiating catalysts afforded the optically active corresponding secondary alcohols in moderate to excellent (up to 98 % op) optical yields.     

Synthesis of new thioxanthenes by organocatalytic intramolecular Friedel–Crafts reaction

An efficient organocatalytic route has been developed to synthesize novel substituted thioxanthenes (2a–2v) starting from diaryl thioether alcohols (1a–1v) using the intramolecular Friedel–Crafts reaction. The starting materials were obtained in two stages via a coupling reaction followed by the Grignard reaction. In this study, we tried for the first time to use some organic Brønsted acids as organocatalysts (3a–3h) in the intramolecular Friedel–Crafts cyclization reaction of thioether alcohols. The synthesis of original substituted thioxanthenes was achieved within 15?minutes by using N-triflylphosphoramide (3h) with quantitative yields in THF at room temperature.     

Oxidation of Benzylic Alcohols to Carbonyl Compounds with Potassium Permanganate in Ionic Liquids

Abstract

The selective oxidation of primary and secondary benzylic alcohols with potassium permanganate in ionic liquids to give corresponding aldehydes and ketones in 83–97% yields has been described.     

NHC-coordinated palladacycle catalyzed 1,2-addition of arylboronates to unactivated ketones

Abstract

Palladium catalyzed intermolecular 1,2-addition of arylboronate to unactivated ketone was investigated. NHC-coordinated palladacycle 4c exhibited catalytic activity for the reactions and provided the corresponding tertiary alcohols and γ,γ-disubstituted γ-lactones in good to excellent yields.     

Metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into aromatic amides with molecular iodine in aq ammonia, and hydrogen peroxide

Various primary alcohols, particularly benzylic alcohols, could be converted into the corresponding aromatic amides in good yields in a one-pot manner by treatment with molecular iodine in aq. NH₃, followed by reaction with ∼30% aq H₂O₂. Similarly, various benzylic halides could be also converted into the corresponding aromatic amides in good yields in a one-pot manner by treatment with molecular iodine in aq NH₃, followed by reaction with ∼30% aq H₂O₂. The present reactions involve the metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into the corresponding aromatic amides, respectively.